Patent GB-989759-A (GB)
Title: Production of 1,3,4-thiadiazoles
Inventor: WEIDINGER HANS
IPC: C09B1/06
Filed: 1963-02-20
Abstract: In a process for the production of 1,3,4-thiadiazoles a monothiodiacyl hydrazine having the formula <FORM:0989759/C2/1> in which R1 denotes a hydrogen atom or an aliphatic, cycloaliphatic, araliphatic, non-vattable aromatic or heterocyclic radical, any of which may be substituted by groups or atoms which are inert under the reaction conditions or the radical <FORM:0989759/C2/2> in which R denotes an alkylene or phenylene radical and R2 denotes an aliphatic, cycloaliphatic, araliphatic, non-vattable aromatic or heterocyclic radical, any of which may be substituted by groups or atoms which are inert under the reaction conditions, or the radical <FORM:0989759/C2/3> in which R denotes an alkylene or phenylene radical and R1 has the meaning given above, on the reaction mixture obtained by reacting an appropriate carboxylic acid hydrazide with dithiocarboxylic acids or esters thereof, thiocarboxylic acid esters, N-succinyl-thiocarboxylic amides or N - phthalythiocarboxylic amides, is heated in a solvent at 20 DEG  to 150 DEG  C., preferably 50 DEG to 100 DEG  C.  Examples relate to the preparation of 2,5-diphenyl-; 2-phenyl-5-[41 - nitrophenyl]-; 2 - phenyl - 5 - [41 - aminophenyl]-; 2 - phenyl - 5 - [21 - hydroxyphenyl]-; 2 - phenyl - 5 - [g  - pyridyl] -; 2 - methyl - 5 - phenyl-; 2-cyanoethyl-5-phenyl-; 2-phenyl-5-[31 - cyano - phenyl] - ; 2 - [p - nitrophenyl] - 5 - [p - chlorophenyl] - ; 2 - phenyl - 5 - [p - chlorophenyl]- ; 2-[o-hydroxyphenyl] -5-[p-methoxyphenyl] - ; 2 - phenyl - 5 - [p - methoxyphenyl]- and 2 - phenyl - 1,3,4 - thiadiazoles and various anthraquinone dyes (see Division C4). Monothiodiacyl hydrazines employed as starting materials may be prepared by reacting carboxylic hydrazides with dithiocarboxylic acids or esters thereof, thiocarboxylic acid esters, N-succinylthiocarboxylic amides or N-phthalythiocarboxylic amides.  Thiobenzoyl hydrazine is obtained by reacting thiobenzoic acid ethyl ester with benzoic acid hydrazide.  N - phthalyl - p - chlorothiobenzamide is obtained by reacting phthalyl chloride with p-chlorothiobenzamide.  N - phthalyl - p - methoxythiobenzamide is obtained by an analogous process.  N,N1 - diphthalyldithioterephthalic diamide is obtained by reacting phthalyl chloride with dithioterephthalic diamide.ALSO:The invention comprises 2-[11-amino-21-anthraquinonyl] - 5 - phenyl - 1,3,4 - thiadiazole, 2 - [11,41 - diamino - 21 - anthraquinonyl] - 5 - phenyl - 1,3,4 - thiadiazole and the compounds of the formulae <FORM:0989759/C4-C5/1> and a process from the production of 1,3,4-thiadiazoles wherein a monothiodiacylhydrazine having the general formula <FORM:0989759/C4-C5/2> in which R1 denotes a hydrogen atom or an aliphatic, cycloaliphatic, araliphatic, vattable on non-vattable heterocyclic radical, any of which may be substituted by groups or atoms which are inert under the reaction conditions or the radical <FORM:0989759/C4-C5/3> in which R denotes an alkylene or phenylene radical and R2 denotes an aliphatic, cycloaliphatic, aliphatic, araliphatic, vattable or non-vattable aromatic or heterocyclic radical any of which may be substituted by groups or atoms which are inert under the reaction conditions or the radical <FORM:0989759/C4-C5/4> in which R denotes an alkylene or phenylene radical and R1 has the meaning given above, on the reaction mixture obtained by reacting an appropriate carboxylic acid hydrazide with dithiocarboxylic acids or esters thereof, thiocarboxylic acid esters, N-succinyl thiocarboxylic amides or N-phtholyl-thiocarboxylic amides, is heated in a solvent at 20 DEG  to 150 DEG  C., preferably at 50 DEG  to 100 DEG  C.  In Example (14) 2-[11-amino-21 - anthraquinonyl] - 5 - phenyl - 1,3,4 - thiadiazole is obtained by reacting N-phthalyl thiobenzamide with 1-amino-anthraquinone-2-carboxylic acid hydrazide in the presence of N-methylpyrrolidone with subsequent addition of p-toluene sulphonic acid and heating the compound dyes cotton bluish red shades. Additional examples are furnished and starting materials listed.